Laundry detergent composition comprising a particle having hueing agent and clay

ABSTRACT

The present invention relates to a laundry detergent composition comprising a particle comprising hueing agent and clay. The particle can be incorporated into laundry detergent products, such as a laundry detergent powder. The particle exhibits an excellent storage stability profile with very little bleeding of the hueing dye from the particle, exhibits excellent fabric deposition of the hueing dye during a laundering process without causing any spot staining of the fabric, and does not impact the visual appearance of a laundry detergent powder when incorporated therein.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims priority to U.S. Provisional Patent ApplicationNo. 61/644,480, entitled “A Laundry Detergent Composition Comprising AParticle Having Hueing Agent and Clay,” which was filed on May 9, 2012,and is entirely incorporated by reference herein.

FIELD OF THE INVENTION

The present invention relates to a laundry detergent compositioncomprising a particle comprising hueing agent and clay. The particle canbe incorporated into laundry detergent products, such as a laundrydetergent powder. The particle exhibits an excellent storage stabilityprofile with very little bleeding of the hueing dye from the particle,exhibits excellent fabric deposition of the hueing dye during alaundering process without causing any spot staining of the fabric, anddoes not impact the visual appearance of a laundry detergent powder whenincorporated therein.

BACKGROUND OF THE INVENTION

As textile substrates age, their color tends to fade or yellow due toexposure to light, air, soil, and natural degradation of the fibers thatcomprise the substrates. To counteract this unwanted effect, laundrydetergent manufacturers incorporate hueing agents into their products.Thus, the purpose of hueing agents is typically to visually brightenthese textile substrates and counteract the fading and yellowing of thetextile substrates.

Detergent manufacturers continue to seek to incorporate hueing dyes intotheir laundry detergent products, especially their laundry detergentpowders. Detergent manufacturers prefer to incorporate detergentingredients into a spray-dried laundry detergent base powder, bycrutching and spray-drying the detergent ingredients: as this is an easyand cost effective means for their incorporation. However, when hueingdyes are incorporated into the crutcher, their colour determines thecolour of the spray-dried laundry detergent base powder, which may notbe preferred by the consumer. This has led detergent manufacturers todesign separate particles for their hueing dyes.

These particles need to exhibit good storage stability, especially inconditions of high humidity, the dye must not bleed out of the particleand affect the colour of the base laundry powder, this is especiallyimportant in the presence of non-ionic detersive surfactant that may bepresent in the detergent formulation, and especially when sprayed ontothe bulk of the powder.

These hueing dye particles must still rapidly dissolve in water, evencold water, during the laundering process, and the particles mustrapidly deposit dye onto the fabric without causing dye damage such asspot staining. The inventors have found that a unique combination of aspecific type of hueing dye, when incorporated into a particle thatadditionally comprises clay, the resultant particle exhibits both goodstorage stability profile, good fabric deposition and does not impactthe visual appearance of the base detergent powder when admixed thereto.The particle exhibits an excellent storage stability profile with verylittle bleeding of the hueing dye from the particle, exhibits excellentfabric deposition of the hueing dye during a laundering process withoutcausing any spot staining of the fabric, and does not impact the visualappearance of a laundry detergent powder when incorporated therein.

SUMMARY OF THE INVENTION

A laundry detergent composition comprising a particle, wherein theparticle comprises: (a) hueing agent, wherein the hueing agent has thefollowing structure:

wherein: R₁ and R₂ are independently selected from the group consistingof: H; alkyl; alkoxy; alkyleneoxy; alkyl capped alkyleneoxy; urea; andamido; R₃ is a substituted aryl group; X is a substituted groupcomprising sulfonamide moiety and optionally an alkyl and/or arylmoiety, and wherein the substituent group comprises at least onealkyleneoxy chain that comprises an average molar distribution of atleast four alkyleneoxy moieties; (b) clay; and (c) another detergentingredient.

A particle comprising: (a) hueing agent, wherein the hueing agent hasthe following structure:

wherein:R₁ and R₂ are independently selected from the group consisting of: H;alkyl; alkoxy; alkyleneoxy; alkyl capped alkyleneoxy; urea; and amido;R₃ is a substituted aryl group;X is a substituted group comprising sulfonamide moiety and optionally analkyl and/or aryl moiety, and wherein the substituent group comprises atleast one alkyleneoxy chain that comprises an average molar distributionof at least four alkyleneoxy moieties; and (b) clay.

A particle comprising: (a) hueing agent, wherein the hueing agent hasthe following structure:

wherein:R₁ and R₂ are independently selected from the group consisting of: H;alkyl; alkoxy; alkyleneoxy; alkyl capped alkyleneoxy; urea; and amido;R₃ is a substituted aryl group;X is a substituted group comprising sulfonamide moiety and optionally analkyl and/or aryl moiety, and wherein the substituent group comprises atleast one alkyleneoxy chain that comprises an average molar distributionof at least four alkyleneoxy moieties; and (b) natural clay.

A particle comprising: (a) hueing agent, wherein the hueing agent hasthe following structure:

wherein:R₁ and R₂ are independently selected from the group consisting of: H;alkyl; alkoxy; alkyleneoxy; alkyl capped alkyleneoxy; urea; and amido;R₃ is a substituted aryl group;X is a substituted group comprising sulfonamide moiety and optionally analkyl and/or aryl moiety, and wherein the substituent group comprises atleast one alkyleneoxy chain that comprises an average molar distributionof at least four alkyleneoxy moieties; and (b) natural bentonite clay.

DETAILED DESCRIPTION OF THE INVENTION

Particle:

The particle comprises hueing agent and clay. The hueing dye and clayare described in more detail below.

The particle preferably comprises from 0.0001 wt % to 4 wt % hueing dye,from 0.0001 wt % to 2 wt % hueing dye, from 0.0001 wt % to 1 wt % hueingdye, from 0.0001 wt % to 0.1 wt %, or even from 0.0001 wt % to 0.01 wt %hueing dye. The particle preferably comprises from 66% to 99.999 wt %clay, and preferably from 80 wt %, or even 90 wt % clay. The particlemay comprise other ingredients, such as the solvent used to carry thehueing dye during the process of preparing the particle: such suitablesolvents include any soluble or miscible material that is not a solid atroom temperature, the solvent may be a liquid or a wax in its pure format room temperature. The particle preferably comprises up to 33 wt %solvent, and preferably up to from 20 wt %, and more preferably up to 20wt %, and more preferably up to 10%, and more preferably up to 5%, oreven up to 4 wt % solvent. Some examples of suitable solvents includealkoxylated aromatic compounds (such as alkoxylates of m-toluidine),glycols (such as polyethylene glycol), alcohols (such as ethanol,propanol, hexanol, and butanol), solvents having a boiling point above60° C. (such as dipropyl ether, ethylene glycol dimethyl ether, andtoluene), and the like, and mixtures thereof. The alkoxylated form ofm-toluidine may be alkoxylated with one or more of the following groups:ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), and anymixtures thereof. The average number of groups forming the alkoxylatedportion of m-toluidine may be from about 1 to about 200, more preferablyfrom about 1 to about 100, and most preferably from about 1 to about 50.The average number of ethylene oxide moieties forming the polyethyleneglycol may be in the range of from about 1 to 200, preferably from 1 to100, or even from 1 to 50. The particle may comprise other detergentingredients, suitable detergent ingredients are described in more detailbelow.

The particle may have a weight average particle size of from 50micrometers to 2,000 micrometers, preferably from 50 micrometers to1,500 micrometers, or from 50 micrometers to 1,000 micrometers, or from50 micrometers to 500 micrometers, or from 50 micrometer to 300micrometers, or from 50 to 200 micrometers.

Laundry Detergent Composition:

The laundry detergent composition comprises the particle described inmore detail above. The composition can be in any form, for example aliquid including gels, unit dose including tablet and pouch form, andsolid form including solid particulate form. Typically, the compositionis a fully formulated laundry detergent composition, not a portionthereof such as a spray-dried or agglomerated particle that only formspart of the laundry detergent composition. Preferably, the compositionis in solid form, more preferably the composition is in solidfree-flowing particulate form: preferably the composition is in the formof free flowing laundry detergent particles.

Typically, the composition comprises a plurality of chemically differentparticles, such as spray-dried base detergent particles and/oragglomerated base detergent particles and/or extruded base detergentparticles, in combination with one or more, typically two or more, orthree or more, or four or more, or five or more, or six or more, or eventen or more particles selected from: surfactant particles, includingsurfactant agglomerates, surfactant extrudates, surfactant needles,surfactant noodles, surfactant flakes; polymer particles such ascellulosic polymer particles, polyester particles, polyamine particles,terephthalate polymer particles, polyethylene glycol polymer particles;builder particles, such as sodium carbonate and sodium silicateco-builder particles, phosphate particles, zeolite particles, silicatesalt particles, carbonate salt particles; filler particles such assulphate salt particles; dye transfer inhibitor particles; dye fixativeparticles; bleach particles, such as percarbonate particles, especiallycoated percarbonate particles, such as percarbonate coated withcarbonate salt, sulphate salt, silicate salt, borosilicate salt, or anycombination thereof, perborate particles, bleach catalyst particles suchas transition metal bleach catalyst particles, or oxaziridinium-basedbleach catalyst particles, pre-formed peracid particles, especiallycoated pre-formed peracid particles, and co-bleach particles of bleachactivator, source of hydrogen peroxide and optionally bleach catalyst;bleach activator particles such as oxybenzene sulphonate bleachactivator particles and tetra acetyl ethylene diamine bleach activatorparticles; chelant particles such as chelant agglomerates; hueing dyeparticles; brightener particles; enzyme particles such as proteaseprills, lipase prills, cellulase prills, amylase prills, mannanaseprills, pectate lyase prills, xyloglucanase prills, bleaching enzymeprills, cutinase prills and co-prills of any of these enzymes; clayparticles such as montmorillonite particles or particles of clay andsilicone; flocculant particles such as polyethylene oxide particles; waxparticles such as wax agglomerates; perfume particles such as perfumemicrocapsules, especially melamine formaldehyde-based perfumemicrocapsules, starch encapsulated perfume accord particles, andpro-perfume particles such as Schiff base reaction product particles;aesthetic particles such as coloured noodles or needles or lamellaeparticles, and soap rings including coloured soap rings; and anycombination thereof.

Detergent Ingredients:

The composition typically comprises detergent ingredients. Suitabledetergent ingredients include: detersive surfactants including anionicdetersive surfactants, non-ionic detersive surfactants, cationicdetersive surfactants, zwitterionic detersive surfactants, amphotericdetersive surfactants, and any combination thereof; polymers includingcarboxylate polymers, polyethylene glycol polymers, polyester soilrelease polymers such as terephthalate polymers, amine polymers,cellulosic polymers, dye transfer inhibition polymers, dye lock polymerssuch as a condensation oligomer produced by condensation of imidazoleand epichlorhydrin, optionally in ratio of 1:4:1, hexamethylenediaminederivative polymers, and any combination thereof; builders includingzeolites, phosphates, citrate, and any combination thereof; buffers andalkalinity sources including carbonate salts and/or silicate salts;fillers including sulphate salts and bio-filler materials; bleachincluding bleach activators, sources of available oxygen, pre-formedperacids, bleach catalysts, reducing bleach, and any combinationthereof; chelants; photobleach; hueing agents; brighteners; enzymesincluding proteases, amylases, cellulases, lipases, xylogucanases,pectate lyases, mannanases, bleaching enzymes, cutinases, and anycombination thereof; fabric softeners including clay, silicones,quaternary ammonium fabric-softening agents, and any combinationthereof; flocculants such as polyethylene oxide; perfume includingstarch encapsulated perfume accords, perfume microcapsules, perfumeloaded zeolites, schif base reaction products of ketone perfume rawmaterials and polyamines, blooming perfumes, and any combinationthereof; aesthetics including soap rings, lamellar aesthetic particles,geltin beads, carbonate and/or sulphate salt speckles, coloured clay,and any combination thereof: and any combination thereof.

Hueing Agent.

The hueing agent has the following structure:

wherein: R₁ and R₂ are independently selected from the group consistingof: H; alkyl, preferably C₁ to C₁₀ alkyl; alkoxy, preferably C₁ to C₁₀alkoxy; alkyleneoxy; alkyl capped alkyleneoxy; urea; and amido; R₃ is asubstituted aryl group; X is a substituted group comprising sulfonamidemoiety and optionally an alkyl, preferably C₁ to C₁₀ alkyl, and/or arylmoiety, and wherein the substituent group comprises at least onealkyleneoxy chain that comprises an average molar distribution of atleast four alkyleneoxy moieties.

Preferably, the hueing agent has the following structure:

wherein: R₁ and R₂ are independently selected from the group consistingof: H; alkyl, preferably C₁ to C₁₀ alkyl; alkoxy, preferably C₁ to C₁₀alkoxy; alkyleneoxy; alkyl capped alkyleneoxy; urea; and amido; U is ahydrogen, a substituted or unsubstituted amino group; W is a substitutedgroup comprising an amino moiety and optionally an alkyl, preferably C₁to C₁₀ alkyl, and/or aryl moiety, and wherein the substituted groupcomprises at least one alkyleneoxy chain that comprises an average molardistribution of at least four alkyleneoxy moieties; Y is a hydrogen or asulfonic acid moiety; and Z is a sulfonic acid moiety or an amino groupsubstituted with an aryl group or an alkyl group, preferably a C₁ to C₁₀alkyl group.

Preferably, R₁ is an alkoxy group, preferably C₁ to C₁₀ alkoxy, and R₂is an alkyl group, preferably C₁ to C₁₀ alkyl.

Suitable hueing agents include, but are not limited to, the followingstructures:

Clay:

The particle is comprised of a clay carrier and a hueing dye. Theparticle may be comprised of a majority by weight of the carrier.Typically, the clay carrier is selected from the group consisting of:allophane clays; chlorite clays, preferred chlorite clays are amesiteclays, baileychlore clays, chamosite clays, clinochlore clays, cookeiteclays, corundophite clays, daphnite clays, delessite clays, gonyeriteclays, nimite clays, odinite clays, orthochamosite clays, pannantiteclays, penninite clays, rhipidolite clays, sudoite clays and thuringiteclays; illite clays; inter-stratified clays; iron oxyhydroxide clays,preferred iron oxyhydroxide clays are hematite clays, goethite clays,lepidocrite clays and ferrihydrite clays; kaolin clays, preferred kaolinclays are kaolinite clays, halloysite clays, dickite clays, nacriteclays and hisingerite clays; smectite clays; vermiculite clays; andmixtures thereof. Other examples of clay carriers include sepiolite,alunite, hydrotalcite, attapulgite, pimelite, muscovite, willemseite,minnesotaite, antigorite, amesite, china clay, halloysite, and the like,and combinations of any of the foregoing clay carriers.

Preferably, the clay is a smectite clay. Preferred smectite clays arebeidellite clays, hectorite clays, laponite clays, montmorilloniteclays, nontonite clays, nontronite clays, saponite clays and mixturesthereof. Preferably, the smectite clay may be a dioctahedral smectiteclay. A preferred dioctahedral smectite clay is montmorillonite clay.The montmorillonite clay may be low-charge montmorillonite clay (alsoknown as sodium montmorillonite clay or Wyoming-type montmorilloniteclay). Typically, low-charge montmorillonite clay can be represented bythe formula:Na_(x)Al_(2-x)Mg_(x)Si₄O₁₀(OH)₂,wherein, x is a number from 0.1 to 0.5, preferably from 0.2, andpreferably to 0.4.

The montmorillonite clay may also be a high-charge montmorillonite clay(also known as a calcium montmorillonite clay or Cheto-typemontmorillonite clay). Typically, high-charge montmorillonite clays canbe represented by the formula:Ca_(x)Al_(2-x)Mg_(x)Si₄O₁₀(OH)₂,wherein, x is a number from 0.1 to 0.5, preferably from 0.2, andpreferably to 0.4.

Bentonites are clays that are comprised primarily of, and whoseproperties are typically dictated by a smectite clay mineral (e.g.montmorillonite, hectorite, nontronite, etc.). Smectites are generallycomprised of stacks of negatively charged layers (wherein each layer iscomprised of two tetrahedral sheets attached to one octahedral sheet;the tetrahedra formed by silicon and oxygen atoms and the octahedralformed by aluminum and oxygen atoms together with hydroxyl radicals)balanced and/or compensated by alkaline earth metal cations (e.g. Ca²⁺and/or Mg²⁺) and/or alkali metal cations (eg. Na⁺ and/or K⁺). Therelative amounts of the two types (alkaline earth metal and alkalimetal) of cations typically determine the swelling characteristic of theclay material when placed in water. Bentonites, in which the alkalineearth metal cation Ca²⁺ is predominant (or is in a relative majority),are called calcium bentonites; whereas, bentonites in which the alkalimetal cation Na⁺ is predominant (or is in a relative majority) arecalled sodium bentonites. A preferred clay is bentonite clay, whichcomprises predominantly montmorillonite clay.

The term “natural,” as used herein with respect to clay material, refersto the presence of the mineral in deposits found in the earth (formedvia modification of volcanic ash deposits in marine basins by geologicalprocesses). Accordingly, a natural deposit of bentonite containingprimarily (or a relative majority of) Na⁺ cations is referred to as“natural sodium bentonite;” whereas, a natural deposit of a bentonitepredominantly containing (or containing a relative majority of) Ca²⁺cations is referred to as “natural calcium bentonite.”

Synthetic analogues of Na and Ca bentonite may also be synthesized (byusing hydrothermal techniques, for example). “Synthetic sodiumbentonite” may also refer to bentonite obtained by treatment of calciumbentonite with, but not limited to, sodium carbonate or sodium oxalate(to remove the calcium ion and substitute it with a sodium ion). Thistreatment can be varied to impart different levels of ion-exchange orNa⁺ for Ca²⁺ substitution. Herein, these materials are referred to as“partially activated” and “fully activated” grades of clay material,respectively (with “fully” referring to maximum exchange of Ca²⁺ forNa⁺).

One of the reasons for converting calcium bentonite into syntheticsodium bentonite is to impart greater swelling properties to otherwise(relatively) non-swelling calcium bentonite. There is also an aestheticbenefit associated with synthetic sodium bentonite that is lacking innatural sodium bentonite. Natural sodium bentonite (generally,irrespective of the part of the world in which the deposit is located)is colored. The color ranges from brown to yellow to gray. Bycomparison, natural calcium bentonite has a more aesthetically pleasingwhite color. Consequently, synthetic sodium bentonite that is obtainedby treatment of this white calcium bentonite is also white. As a result,natural calcium bentonite and synthetic sodium bentonite find morewidespread use in the detergent industry, as compared to natural sodiumbentonite.

Applicants' studies have shown differences in the propensity of certainhueing agents to stain fabrics depending on the type of bentonite clay(in the form of a colored clay speckle or colored clay powder) to whichthe hueing agents have been applied (natural sodium vs. natural calciumbentonite; natural sodium bentonite vs. synthetic sodium bentonite;partially vs. fully activated synthetic sodium bentonite). It has beendiscovered that, at equal color loading, natural sodium bentonitedisplay lower propensity for staining than calcium bentonite. It hasalso been discovered that, at equal color loading, synthetic sodiumbentonite exhibits lesser staining risk than calcium bentonite. However,at equal color loading, even fully activated synthetic sodium bentoniteshows greater staining than natural sodium bentonite. The sameobservations were made independent of whether the color was applied to abentonite speckle or a bentonite powder.

However, the appearance of a particle made from natural sodium bentonitemay need to be improved, due to the yellow/gray/brown coloration of thenatural sodium bentonite. The reduction in the staining risk observed bythe use of natural sodium bentonite indicates that it may be possible toblend natural sodium bentonite with a whiter bentonite (such as calciumbentonite or synthetic sodium bentonite or mixtures thereof), therebyresulting in a speckle with a whiter appearance than a 100% naturalNa-bentonite speckle, but with lower staining risk than 100% Ca andsynthetic sodium Bentonite speckles.

In one aspect, the clay carrier exhibits a particular range of particlesize, as determined, for example, by sieving techniques according toASTM D1921-06 (“Standard Test Method For Particle Size (Sieve Analysis)of Plastic Materials”). Alternative methods known to those skilled inthe art may also be utilized for determining particle size. For example,other sieving techniques may be used or electronic laboratory equipmentknown for determining particle size may alternatively be employed.

Commercially available examples of suitable clay carriers includePelben® 10 and Pelben® 35 (available from Buntech, a Brazilian company).Suitable examples of clay powders include Argel® 10 and Argel® 40(available from Buntech).

Suitable clays also include clays supplied by Amcol, Ill., UnitedStates, such as those sold under the tradenames Quest® Bentonite andPolargel® series of clay.

The clay carrier can be characterized by having a particle size suchthat at least 95 wt % of the clay carrier has a particle size that is inthe range from 50 micrometers to 2,000 micrometers, preferably from 50micrometers to 1,500 micrometers, or from 50 micrometers to 1,000micrometers, or from 50 micrometers to 500 micrometers, or from 50micrometer to 300 micrometers, or from 50 to 200. Further preferably theclay carrier can be characterized by having an average particle of 50micrometers to 2,000 micrometers, preferably from 50 micrometers to1,500 micrometers, or from 50 micrometers to 1,000 micrometers, or from50 micrometers to 500 micrometers, or from 50 micrometer to 300micrometers, or from 50 to 200. The clay preferably has a particle sizesuch that at least 95 wt % of the clay has a particle size in the rangeof from 50 micrometers to 400 micrometers, preferably 50 micrometers to300 or more preferably 100 to 250 micrometers or from 50 to 200micrometers.

The clay may also impart fabric softness benefits during a launderingprocess.

Detersive Surfactant:

Suitable detersive surfactants include anionic detersive surfactants,non-ionic detersive surfactant, cationic detersive surfactants,zwitterionic detersive surfactants, amphoteric detersive surfactants,and any combination thereof.

Anionic Detersive Surfactant:

Suitable anionic detersive surfactants include sulphate and sulphonatedetersive surfactants.

Suitable sulphonate detersive surfactants include alkyl benzenesulphonate, such as C₁₀₋₁₃ alkyl benzene sulphonate. Suitable alkylbenzene sulphonate (LAS) is obtainable, or even obtained, bysulphonating commercially available linear alkyl benzene (LAB); suitableLAB includes low 2-phenyl LAB, such as those supplied by Sasol under thetradename Isochem® or those supplied by Petresa under the tradenamePetrelab®, other suitable LAB include high 2-phenyl LAB, such as thosesupplied by Sasol under the tradename Hyblene®. Another suitable anionicdetersive surfactant is alkyl benzene sulphonate that is obtained byDETAL catalyzed process, although other synthesis routes, such as HF,may also be suitable.

Suitable sulphate detersive surfactants include alkyl sulphate, such asC₈₋₁₈ alkyl sulphate, or predominantly C₁₋₂ alkyl sulphate. The alkylsulphate may be derived from natural sources, such as coco and/ortallow. Alternative, the alkyl sulphate may be derived from syntheticsources such as C₁₂₋₁₅ alkyl sulphate.

Another suitable sulphate detersive surfactant is alkyl alkoxylatedsulphate, such as alkyl ethoxylated sulphate, or a C₈₋₄₈ alkylalkoxylated sulphate, or a C₈₋₄₈ alkyl ethoxylated sulphate. The alkylalkoxylated sulphate may have an average degree of alkoxylation of from0.5 to 20, or from 0.5 to 10. The alkyl alkoxylated sulphate may be aC₈₋₄₈ alkyl ethoxylated sulphate, typically having an average degree ofethoxylation of from 0.5 to 10, or from 0.5 to 7, or from 0.5 to 5 orfrom 0.5 to 3.

The alkyl sulphate, alkyl alkoxylated sulphate and alkyl benzenesulphonates may be linear or branched, substituted or un-substituted.

The anionic detersive surfactant may be a mid-chain branched anionicdetersive surfactant, such as a mid-chain branched alkyl sulphate and/ora mid-chain branched alkyl benzene sulphonate.

The mid-chain branches are typically C₁₋₄ alkyl groups, such as methyland/or ethyl groups.

Another suitable anionic detersive surfactant is alkyl ethoxycarboxylate.

The anionic detersive surfactants are typically present in their saltform, typically being complexed with a suitable cation. Suitablecounter-ions include Na⁺ and K⁺, substituted ammonium such as C₁-C₆alkanolammonium such as mono-ethanolamine (MEA) tri-ethanolamine (TEA),di-ethanolamine (DEA), and any mixture thereof.

Non-Ionic Detersive Surfactant:

Suitable non-ionic detersive surfactants are selected from the groupconsisting of: C₈-C₁₈ alkyl ethoxylates, such as, NEODOL® non-ionicsurfactants from Shell; C₆-C₁₂ alkyl phenol alkoxylates whereinoptionally the alkoxylate units are ethyleneoxy units, propyleneoxyunits or a mixture thereof; C₁₂-C₁₈ alcohol and C₆-C₁₂ alkyl phenolcondensates with ethylene oxide/propylene oxide block polymers such asPluronic® from BASF; C₁₄-C₂₂ mid-chain branched alcohols; C₁₄-C₂₂mid-chain branched alkyl alkoxylates, typically having an average degreeof alkoxylation of from 1 to 30; alkylpolysaccharides, such asalkylpolyglycosides; polyhydroxy fatty acid amides; ether cappedpoly(oxyalkylated) alcohol surfactants; and mixtures thereof.

Suitable non-ionic detersive surfactants are alkyl polyglucoside and/oran alkyl alkoxylated alcohol.

Suitable non-ionic detersive surfactants include alkyl alkoxylatedalcohols, such as C₈₋₁₈ alkyl alkoxylated alcohol, or a C₈₋₁₈ alkylethoxylated alcohol. The alkyl alkoxylated alcohol may have an averagedegree of alkoxylation of from 0.5 to 50, or from 1 to 30, or from 1 to20, or from 1 to 10. The alkyl alkoxylated alcohol may be a C₈₋₁₈ alkylethoxylated alcohol, typically having an average degree of ethoxylationof from 1 to 10, or from 1 to 7, or from 1 to 5, or from 3 to 7. Thealkyl alkoxylated alcohol can be linear or branched, and substituted orun-substituted.

Suitable nonionic detersive surfactants include secondary alcohol-baseddetersive surfactants having the formula:

wherein R¹=linear or branched, substituted or unsubstituted, saturatedor unsaturated C₂₋₈ alkyl;wherein R²=linear or branched, substituted or unsubstituted, saturatedor unsaturated C₂₋₈ alkyl,wherein the total number of carbon atoms present in R¹+R² moieties is inthe range of from 7 to 13;wherein EO/PO are alkoxy moieties selected from ethoxy, propoxy, ormixtures thereof, optionally the EO/PO alkoxyl moieties are in random orblock configuration;wherein n is the average degree of alkoxylation and is in the range offrom 4 to 10.

Other suitable non-ionic detersive surfactants include EO/PO blockco-polymer surfactants, such as the Plurafac® series of surfactantsavailable from BASF, and sugar-derived surfactants such as alkylN-methyl glucose amide.

Cationic Detersive Surfactant:

Suitable cationic detersive surfactants include alkyl pyridiniumcompounds, alkyl quaternary ammonium compounds, alkyl quaternaryphosphonium compounds, alkyl ternary sulphonium compounds, and mixturesthereof.

Suitable cationic detersive surfactants are quaternary ammoniumcompounds having the general formula:(R)(R₁)(R₂)(R₃)N⁺X⁻wherein, R is a linear or branched, substituted or unsubstituted C₆₋₁₈alkyl or alkenyl moiety, R₁ and R₂ are independently selected frommethyl or ethyl moieties, R₃ is a hydroxyl, hydroxymethyl or ahydroxyethyl moiety, X is an anion which provides charge neutrality,suitable anions include: halides, such as chloride; sulphate; andsulphonate. Suitable cationic detersive surfactants are mono-C₆₋₁₈ alkylmono-hydroxyethyl di-methyl quaternary ammonium chlorides. Suitablecationic detersive surfactants are mono-C₈₋₁₀ alkyl mono-hydroxyethyldi-methyl quaternary ammonium chloride, mono-C₁₀₋₁₂ alkylmono-hydroxyethyl di-methyl quaternary ammonium chloride and mono-C₁₀alkyl mono-hydroxyethyl di-methyl quaternary ammonium chloride.Zwitterionic and/or Amphoteric Detersive Surfactant:

Suitable zwitterionic and/or amphoteric detersive surfactants includeamine oxide such as dodecyldimethylamine N-oxide, alkanolaminesulphobetaines, coco-amidopropyl betaines, HN⁺—R—CO₂ ⁻ basedsurfactants, wherein R can be any bridging group, such as alkyl, alkoxy,aryl or amino acids.

Polymer:

Suitable polymers include carboxylate polymers, polyethylene glycolpolymers, polyester soil release polymers such as terephthalatepolymers, amine polymers, cellulosic polymers, dye transfer inhibitionpolymers, dye lock polymers such as a condensation oligomer produced bycondensation of imidazole and epichlorhydrin, optionally in ratio of1:4:1, hexamethylenediamine derivative polymers, and any combinationthereof.

Carboxylate Polymer:

Suitable carboxylate polymers include maleate/acrylate random copolymeror polyacrylate homopolymer. The carboxylate polymer may be apolyacrylate homopolymer having a molecular weight of from 4,000 Da to9,000 Da, or from 6,000 Da to 9,000 Da. Other suitable carboxylatepolymers are co-polymers of maleic acid and acrylic acid, and may have amolecular weight in the range of from 4,000 Da to 90,000 Da.

Other suitable carboxylate polymers are co-polymers comprising: (i) from50 to less than 98 wt % structural units derived from one or moremonomers comprising carboxyl groups; (ii) from 1 to less than 49 wt %structural units derived from one or more monomers comprising sulfonatemoieties; and (iii) from 1 to 49 wt % structural units derived from oneor more types of monomers selected from ether bond-containing monomersrepresented by formulas (I) and (II):

Formula (I):

wherein in formula (I), R₀ represents a hydrogen atom or CH₃ group, Rrepresents a CH₂ group, CH₂CH₂ group or single bond, X represents anumber 0-5 provided X represents a number 1-5 when R is a single bond,and R₁ is a hydrogen atom or C₁ to C₂₀ organic group;Formula (II)

in formula (II), R₀ represents a hydrogen atom or CH₃ group, Rrepresents a CH₂ group, CH₂CH₂ group or single bond, X represents anumber 0-5, and R₁ is a hydrogen atom or C₁ to C₂₀ organic group.Polyethylene Glycol Polymer:

Suitable polyethylene glycol polymers include random graft co-polymerscomprising: (i) hydrophilic backbone comprising polyethylene glycol; and(ii) hydrophobic side chain(s) selected from the group consisting of:C₄-C₂₅ alkyl group, polypropylene, polybutylene, vinyl ester of asaturated C₁-C₆ mono-carboxylic acid, C₁-C₆ alkyl ester of acrylic ormethacrylic acid, and mixtures thereof. Suitable polyethylene glycolpolymers have a polyethylene glycol backbone with random graftedpolyvinyl acetate side chains. The average molecular weight of thepolyethylene glycol backbone can be in the range of from 2,000 Da to20,000 Da, or from 4,000 Da to 8,000 Da. The molecular weight ratio ofthe polyethylene glycol backbone to the polyvinyl acetate side chainscan be in the range of from 1:1 to 1:5, or from 1:1.2 to 1:2. Theaverage number of graft sites per ethylene oxide units can be less than1, or less than 0.8, the average number of graft sites per ethyleneoxide units can be in the range of from 0.5 to 0.9, or the averagenumber of graft sites per ethylene oxide units can be in the range offrom 0.1 to 0.5, or from 0.2 to 0.4. A suitable polyethylene glycolpolymer is Sokalan HP22.

Polyester Soil Release Polymers:

Suitable polyester soil release polymers have a structure as defined byone of the following structures (I), (II) or (III):—[(OCHR¹—CHR²)_(a)—O—OC—Ar—CO—]_(d)  (I)—[(OCHR³—CHR⁴)_(b)—O—OC-sAr—CO—]_(e)  (II)—[(OCHR⁵—CHR⁶)_(c)—OR⁷]_(f)  (III)wherein:a, b and c are from 1 to 200;d, e and f are from 1 to 50;Ar is a 1,4-substituted phenylene;sAr is 1,3-substituted phenylene substituted in position 5 with SO₃Me;Me is H, Na, Li, K, Mg/2, Ca/2, Al/3, ammonium, mono-, di-, tri-, ortetraalkylammonium wherein the alkyl groups are C₁-C₁₈ alkyl or C₂-C₁₀hydroxyalkyl, or any mixture thereof;R¹, R², R³, R⁴, R⁵ and R⁶ are independently selected from H or C₁-C₁₈ n-or iso-alkyl; andR⁷ is a linear or branched C₁-C₁₈ alkyl, or a linear or branched C₂-C₃₀alkenyl, or a cycloalkyl group with 5 to 9 carbon atoms, or a C₈-C₃₀aryl group, or a C₆-C₃₀ arylalkyl group. Suitable polyester soil releasepolymers are terephthalate polymers having the structure of formula (I)or (II) above.

Suitable polyester soil release polymers include the Repel-o-tex seriesof polymers such as Repel-o-tex SF2 (Rhodia) and/or the Texcare seriesof polymers such as Texcare SRA300 (Clariant).

Amine Polymer:

Suitable amine polymers include polyethylene imine polymers, such asalkoxylated polyalkyleneimines, optionally comprising a polyethyleneand/or polypropylene oxide block.

Cellulosic Polymer:

The composition can comprise cellulosic polymers, such as polymersselected from alkyl cellulose, alkyl alkoxyalkyl cellulose, carboxyalkylcellulose, alkyl carboxyalkyl, and any combination thereof. Suitablecellulosic polymers are selected from carboxymethyl cellulose, methylcellulose, methyl hydroxyethyl cellulose, methyl carboxymethylcellulose, and mixtures thereof. The carboxymethyl cellulose can have adegree of carboxymethyl substitution from 0.5 to 0.9 and a molecularweight from 100,000 Da to 300,000 Da. Another suitable cellulosicpolymer is hydrophobically modified carboxymethyl cellulose, such asFinnfix SH-1 (CP Kelco).

Other suitable cellulosic polymers may have a degree of substitution(DS) of from 0.01 to 0.99 and a degree of blockiness (DB) such thateither DS+DB is of at least 1.00 or DB+2DS−DS² is at least 1.20. Thesubstituted cellulosic polymer can have a degree of substitution (DS) ofat least 0.55. The substituted cellulosic polymer can have a degree ofblockiness (DB) of at least 0.35. The substituted cellulosic polymer canhave a DS+DB, of from 1.05 to 2.00. A suitable substituted cellulosicpolymer is carboxymethylcellulose.

Another suitable cellulosic polymer is cationically modifiedhydroxyethyl cellulose.

Dye Transfer Inhibitor Polymer:

Suitable dye transfer inhibitor (DTI) polymers include polyvinylpyrrolidone (PVP), vinyl co-polymers of pyrrolidone and imidazoline(PVPVI), polyvinyl N-oxide (PVNO), and any mixture thereof.

Hexamethylenediamine Derivative Polymers:

Suitable polymers include hexamethylenediamine derivative polymers,typically having the formula:R₂(CH₃)N⁺(CH₂)6N⁺(CH₃)R₂.2X⁻wherein X⁻ is a suitable counter-ion, for example chloride, and R is apoly(ethylene glycol) chain having an average degree of ethoxylation offrom 20 to 30. Optionally, the poly(ethylene glycol) chains may beindependently capped with sulphate and/or sulphonate groups, typicallywith the charge being balanced by reducing the number of X⁻counter-ions, or (in cases where the average degree of sulphation permolecule is greater than two), introduction of Y⁺ counter-ions, forexample sodium cations.Builder:

Suitable builders include zeolites, phosphates, citrates, and anycombination thereof.

Zeolite Builder:

The composition may be substantially free of zeolite builder.Substantially free of zeolite builder typically means comprises from 0wt % to 10 wt %, zeolite builder, or to 8 wt %, or to 6 wt %, or to 4 wt%, or to 3 wt %, or to 2 wt %, or even to 1 wt % zeolite builder.Substantially free of zeolite builder preferably means “no deliberatelyadded” zeolite builder. Typical zeolite builders include zeolite A,zeolite P, zeolite MAP, zeolite X and zeolite Y.

Phosphate Builder:

The composition may be substantially free of phosphate builder.Substantially free of phosphate builder typically means comprises from 0wt % to 10 wt % phosphate builder, or to 8 wt %, or to 6 wt %, or to 4wt %, or to 3 wt %, or to 2 wt %, or even to 1 wt % phosphate builder.Substantially free of zeolite builder preferably means “no deliberatelyadded” phosphate builder. A typical phosphate builder is sodiumtri-polyphosphate (STPP).

Citrate:

A suitable citrate is sodium citrate. However, citric acid may also beincorporated into the composition, which can form citrate in the washliquor.

Buffer and Alkalinity Source:

Suitable buffers and alkalinity sources include carbonate salts and/orsilicate salts and/or double salts such as burkeitte.

Carbonate Salt:

A suitable carbonate salt is sodium carbonate and/or sodium bicarbonate.The composition may comprise bicarbonate salt. It may be suitable forthe composition to comprise low levels of carbonate salt, for example,it may be suitable for the composition to comprise from 0 wt % to 10 wt% carbonate salt, or to 8 wt %, or to 6 wt %, or to 4 wt %, or to 3 wt%, or to 2 wt %, or even to 1 wt % carbonate salt. The composition mayeven be substantially free of carbonate salt; substantially free means“no deliberately added”.

The carbonate salt may have a weight average mean particle size of from100 to 500 micrometers. Alternatively, the carbonate salt may have aweight average mean particle size of from 10 to 25 micrometers.

Silicate Salt:

The composition may comprise from 0 wt % to 20 wt % silicate salt, or to15 wt %, or to 10 wt %, or to 5 wt %, or to 4 wt %, or even to 2 wt %,and may comprise from above 0 wt %, or from 0.5 wt %, or even from 1 wt% silicate salt. The silicate can be crystalline or amorphous. Suitablecrystalline silicates include crystalline layered silicate, such asSKS-6. Other suitable silicates include 1.6R silicate and/or 2.0Rsilicate. A suitable silicate salt is sodium silicate. Another suitablesilicate salt is sodium metasilicate.

Filler:

The composition may comprise from 0 wt % to 70% filler. Suitable fillersinclude sulphate salts and/or bio-filler materials.

Sulphate Salt:

A suitable sulphate salt is sodium sulphate. The sulphate salt may havea weight average mean particle size of from 100 to 500 micrometers,alternatively, the sulphate salt may have a weight average mean particlesize of from 10 to 45 micrometers.

Bio-Filler Material:

A suitable bio-filler material is alkali and/or bleach treatedagricultural waste.

Bleach:

The composition may comprise bleach. Alternatively, the composition maybe substantially free of bleach; substantially free means “nodeliberately added”. Suitable bleach includes bleach activators, sourcesof available oxygen, pre-formed peracids, bleach catalysts, reducingbleach, and any combination thereof. If present, the bleach, or anycomponent thereof, for example the pre-formed peracid, may be coated,such as encapsulated, or clathrated, such as with urea or cyclodextrin.

Bleach Activator:

Suitable bleach activators include: tetraacetylethylenediamine (TAED);oxybenzene sulphonates such as nonanoyl oxybenzene sulphonate (NOBS),caprylamidononanoyl oxybenzene sulphonate (NACA-OBS), 3,5,5-trimethylhexanoyloxybenzene sulphonate (Iso-NOBS), dodecyl oxybenzene sulphonate(LOBS), and any mixture thereof; caprolactams; pentaacetate glucose(PAG); nitrile quaternary ammonium; imide bleach activators, such asN-nonanoyl-N-methyl acetamide; and any mixture thereof.

Source of Available Oxygen:

A suitable source of available oxygen (AvOx) is a source of hydrogenperoxide, such as percarbonate salts and/or perborate salts, such assodium percarbonate. The source of peroxygen may be at least partiallycoated, or even completely coated, by a coating ingredient such as acarbonate salt, a sulphate salt, a silicate salt, borosilicate, or anymixture thereof, including mixed salts thereof. Suitable percarbonatesalts can be prepared by a fluid bed process or by a crystallizationprocess. Suitable perborate salts include sodium perborate mono-hydrate(PB1), sodium perborate tetra-hydrate (PB4), and anhydrous sodiumperborate which is also known as fizzing sodium perborate. Othersuitable sources of AvOx include persulphate, such as oxone. Anothersuitable source of AvOx is hydrogen peroxide.

Pre-Formed Peracid:

A suitable pre-formed peracid is N,N-pthaloylamino peroxycaproic acid(PAP).

Bleach Catalyst:

Suitable bleach catalysts include oxaziridinium-based bleach catalysts,transition metal bleach catalysts and bleaching enzymes.

Oxaziridinium-Based Bleach Catalyst:

A suitable oxaziridinium-based bleach catalyst has the formula:

wherein: R¹ is selected from the group consisting of: H, a branchedalkyl group containing from 3 to 24 carbons, and a linear alkyl groupcontaining from 1 to 24 carbons; R¹ can be a branched alkyl groupcomprising from 6 to 18 carbons, or a linear alkyl group comprising from5 to 18 carbons, R¹ can be selected from the group consisting of:2-propylheptyl, 2-butyloctyl, 2-pentylnonyl, 2-hexyldecyl, n-hexyl,n-octyl, n-decyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-octadecyl,iso-nonyl, iso-decyl, iso-tridecyl and iso-pentadecyl; R² isindependently selected from the group consisting of: H, a branched alkylgroup comprising from 3 to 12 carbons, and a linear alkyl groupcomprising from 1 to 12 carbons; optionally R² is independently selectedfrom H and methyl groups; and n is an integer from 0 to 1.Transition Metal Bleach Catalyst:

The composition may include transition metal bleach catalyst, typicallycomprising copper, iron, titanium, ruthenium, tungsten, molybdenum,and/or manganese cations. Suitable transition metal bleach catalysts aremanganese-based transition metal bleach catalysts.

Reducing Bleach:

The composition may comprise a reducing bleach. However, the compositionmay be substantially free of reducing bleach; substantially free means“no deliberately added”. Suitable reducing bleach include sodiumsulphite and/or thiourea dioxide (TDO).

Co-Bleach Particle:

The composition may comprise a co-bleach particle. Typically, theco-bleach particle comprises a bleach activator and a source ofperoxide. It may be highly suitable for a large amount of bleachactivator relative to the source of hydrogen peroxide to be present inthe co-bleach particle. The weight ratio of bleach activator to sourceof hydrogen peroxide present in the co-bleach particle can be at least0.3:1, or at least 0.6:1, or at least 0.7:1, or at least 0.8:1, or atleast 0.9:1, or at least 1.0:1.0, or even at least 1.2:1 or higher.

The co-bleach particle can comprise: (i) bleach activator, such as TAED;and (ii) a source of hydrogen peroxide, such as sodium percarbonate. Thebleach activator may at least partially, or even completely, enclose thesource of hydrogen peroxide.

The co-bleach particle may comprise a binder. Suitable binders arecarboxylate polymers such as polyacrylate polymers, and/or surfactantsincluding non-ionic detersive surfactants and/or anionic detersivesurfactants such as linear C₁₁-C₁₃ alkyl benzene sulphonate.

The co-bleach particle may comprise bleach catalyst, such as anoxaziridium-based bleach catalyst.

Chelant:

Suitable chelants are selected from: diethylene triamine pentaacetate,diethylene triamine penta(methyl phosphonic acid), ethylenediamine-N′N′-disuccinic acid, ethylene diamine tetraacetate, ethylenediamine tetra(methylene phosphonic acid), hydroxyethane di(methylenephosphonic acid), and any combination thereof. A suitable chelant isethylene diamine-N′N′-disuccinic acid (EDDS) and/or hydroxyethanediphosphonic acid (HEDP). The laundry detergent composition may compriseethylene diamine-N′N′-disuccinic acid or salt thereof. The ethylenediamine-N′N′-disuccinic acid may be in S,S enantiomeric form. Thecomposition may comprise 4,5-dihydroxy-m-benzenedisulfonic acid disodiumsalt. Suitable chelants may also be calcium crystal growth inhibitors.

Calcium Carbonate Crystal Growth Inhibitor:

The composition may comprise a calcium carbonate crystal growthinhibitor, such as one selected from the group consisting of:1-hydroxyethanediphosphonic acid (HEDP) and salts thereof;N,N-dicarboxymethyl-2-aminopentane-1,5-dioic acid and salts thereof;2-phosphonobutane-1,2,4-tricarboxylic acid and salts thereof; and anycombination thereof.

Photobleach:

Suitable photobleaches are zinc and/or aluminium sulphonatedphthalocyanines.

Hueing Agent:

In addition to the hueing dye required by the present invention, otherhueing agents may also be used in combination with the hueing dyedescribed in more detail above to deposit onto fabrics from the washliquor so as to improve fabric whiteness perception, for exampleproducing a relative hue angle of from 200° to 320° on a garment. Thehueing agent is typically blue or violet. It may be suitable that thehueing dye(s) have a peak absorption wavelength of from 550 nm to 650nm, or from 570 nm to 630 nm. The hueing agent may be a combination ofdyes which together have the visual effect on the human eye as a singledye having a peak absorption wavelength on polyester of from 550 nm to650 nm, or from 570 nm to 630 nm. This may be provided for example bymixing a red and green-blue dye to yield a blue or violet shade.

Dyes are typically coloured organic molecules which are soluble inaqueous media that contain surfactants. Dyes maybe selected from theclasses of basic, acid, hydrophobic, direct and polymeric dyes, anddye-conjugates. Suitable polymeric hueing dyes are commerciallyavailable, for example from Milliken, Spartanburg, S.C., USA.

Examples of suitable dyes are, direct violet 7, direct violet 9, directviolet 11, direct violet 26, direct violet 31, direct violet 35, directviolet 40, direct violet 41, direct violet 51, direct violet 66, directviolet 99, acid violet 50, acid blue 9, acid violet 17, acid black 1,acid red 17, acid blue 29, acid blue 80 solvent violet 13, disperseviolet 27 disperse violet 26, disperse violet 28, disperse violet 63 anddisperse violet 77, basic blue 16, basic blue 65, basic blue 66, basicblue 67, basic blue 71, basic blue 159, basic violet 19, basic violet35, basic violet 38, basic violet 48; basic blue 3, basic blue 75, basicblue 95, basic blue 122, basic blue 124, basic blue 141, thiazoliumdyes, reactive blue 19, reactive blue 163, reactive blue 182, reactiveblue 96, Liquitint® Violet CT (Milliken, Spartanburg, USA), Liquitint®Violet DD (Milliken, Spartanburg, USA) and Azo-CM-Cellulose (Megazyme,Bray, Republic of Ireland). Other suitable hueing agents are hueingdye-photobleach conjugates, such as those described in Ref WO09/069,077. A particularly suitable hueing agent is a combination ofacid red 52 and acid blue 80, or the combination of direct violet 9 andsolvent violet 13.

Brightener:

Suitable brighteners are stilbenes, such as C.I. Fluorescent Brightener351 or C.I. Fluorescent Brightener 260. The brightener may be inmicronized particulate form, having a weight average particle size inthe range of from 3 to 30 micrometers, or from 3 micrometers to 20micrometers, or from 3 to 10 micrometers. The brightener can be alpha orbeta crystalline form.

Enzyme:

Suitable enzymes include proteases, amylases, cellulases, lipases,xylogucanases, pectate lyases, mannanases, bleaching enzymes, cutinases,and mixtures thereof.

For the enzymes, accession numbers and IDs shown in parentheses refer tothe entry numbers in the databases Genbank, EMBL and/or Swiss-Prot. Forany mutations, standard 1-letter amino acid codes are used with a *representing a deletion. Accession numbers prefixed with DSM refer tomicro-organisms deposited at Deutsche Sammlung von Mikroorganismen andZellkulturen GmbH, Mascheroder Weg 1b, 38124 Brunswick (DSMZ).

Protease.

The composition may comprise a protease. Suitable proteases includemetalloproteases and/or serine proteases, including neutral or alkalinemicrobial serine proteases, such as subtilisins (EC 3.4.21.62). Suitableproteases include those of animal, vegetable or microbial origin. In oneaspect, such suitable protease may be of microbial origin. The suitableproteases include chemically or genetically modified mutants of theaforementioned suitable proteases. In one aspect, the suitable proteasemay be a serine protease, such as an alkaline microbial protease or/anda trypsin-type protease. Examples of suitable neutral or alkalineproteases include:

(a) subtilisins (EC 3.4.21.62), including those derived from Bacillus,such as Bacillus lentus, Bacillus alkalophilus (P27963, ELYA_BACAO),Bacillus subtilis, Bacillus amyloliquefaciens (P00782, SUBT_BACAM),Bacillus pumilus (P07518) and Bacillus gibsonii (DSM14391).(b) trypsin-type or chymotrypsin-type proteases, such as trypsin (e.g.of porcine or bovine origin), including the Fusarium protease and thechymotrypsin proteases derived from Cellumonas (A2RQE2).(c) metalloproteases, including those derived from Bacillusamyloliquefaciens (P06832, NPRE_BACAM).

Suitable proteases include those derived from Bacillus gibsonii orBacillus Lentus such as subtilisin 309 (P29600) and/or DSM 5483(P29599).

Suitable commercially available protease enzymes include: those soldunder the trade names Alcalase®, Savinase®, Primase®, Durazym®,Polarzyme®, Kannase®, Liquanase®, Liquanase Ultra®, Savinase Ultra®,Ovozyme®, Neutrase®, Everlase® and Esperase® by Novozymes A/S (Denmark);those sold under the tradename Maxatase®, Maxacal®, Maxapem®,Properase®, Purafect®, Purafect Prime®, Purafect Ox®, FN3®, FN4®,Excellase® and Purafect OXP® by Genencor International; those sold underthe tradename Opticlean® and Optimase® by Solvay Enzymes; thoseavailable from Henkel/Kemira, namely BLAP (P29599 having the followingmutations S99D+S101 R+S103A+V104I+G159S), and variants thereof includingBLAP R (BLAP with S3T+V4I+V199M+V205I+L217D), BLAP X (BLAP withS3T+V4I+V205I) and BLAP F49 (BLAP with S3T+V4I+A194P+V199M+V205I+L217D)all from Henkel/Kemira; and KAP (Bacillus alkalophilus subtilisin withmutations A230V+S256G+S259N) from Kao.

Amylase:

Suitable amylases are alpha-amylases, including those of bacterial orfungal origin. Chemically or genetically modified mutants (variants) areincluded. A suitable alkaline alpha-amylase is derived from a strain ofBacillus, such as Bacillus licheniformis, Bacillus amyloliquefaciens,Bacillus stearothermophilus, Bacillus subtilis, or other Bacillus sp.,such as Bacillus sp. NCIB 12289, NCIB 12512, NCIB 12513, sp 707, DSM9375, DSM 12368, DSMZ no. 12649, KSM AP1378, KSM K36 or KSM K38.Suitable amylases include:

(a) alpha-amylase derived from Bacillus licheniformis (P06278,AMY_BACLI), and variants thereof, especially the variants withsubstitutions in one or more of the following positions: 15, 23, 105,106, 124, 128, 133, 154, 156, 181, 188, 190, 197, 202, 208, 209, 243,264, 304, 305, 391, 408, and 444.(b) AA560 amylase (CBU30457, HD066534) and variants thereof, especiallythe variants with one or more substitutions in the following positions:26, 30, 33, 82, 37, 106, 118, 128, 133, 149, 150, 160, 178, 182, 186,193, 203, 214, 231, 256, 257, 258, 269, 270, 272, 283, 295, 296, 298,299, 303, 304, 305, 311, 314, 315, 318, 319, 339, 345, 361, 378, 383,419, 421, 437, 441, 444, 445, 446, 447, 450, 461, 471, 482, 484,optionally that also contain the deletions of D183* and G184*.(c) variants exhibiting at least 90% identity with the wild-type enzymefrom Bacillus SP722 (CBU30453, HD066526), especially variants withdeletions in the 183 and 184 positions.

Suitable commercially available alpha-amylases are Duramyl®, Liquezyme®Termamyl®, Termamyl Ultra®, Natalase®, Supramyl®, Stainzyme®, StainzymePlus®, Fungamyl® and BAN® (Novozymes A/S), Bioamylase® and variantsthereof (Biocon India Ltd.), Kemzym® AT 9000 (Biozym Ges. m.b.H,Austria), Rapidase®, Purastar®, Optisize HT Plus®, Enzysize®, Powerase®and Purastar Oxam®, Maxamyl® (Genencor International Inc.) and KAM®(KAO, Japan). Suitable amylases are Natalase®, Stainzyme® and StainzymePlus®.

Cellulase:

The composition may comprise a cellulase. Suitable cellulases includethose of bacterial or fungal origin. Chemically modified or proteinengineered mutants are included. Suitable cellulases include cellulasesfrom the genera Bacillus, Pseudomonas, Humicola, Fusarium, Thielavia,Acremonium, e.g., the fungal cellulases produced from Humicola insolens,Myceliophthora thermophila and Fusarium oxysporum.

Commercially available cellulases include Celluzyme®, and Carezyme®(Novozymes A/S), Clazinase®, and Puradax HA® (Genencor InternationalInc.), and KAC-500(B)® (Kao Corporation).

The cellulase can include microbial-derived endoglucanases exhibitingendo-beta-1,4-glucanase activity (E.C. 3.2.1.4), including a bacterialpolypeptide endogenous to a member of the genus Bacillus sp. AA349 andmixtures thereof. Suitable endoglucanases are sold under the tradenamesCelluclean® and Whitezyme® (Novozymes A/S, Bagsvaerd, Denmark).

The composition may comprise a cleaning cellulase belonging to GlycosylHydrolase family 45 having a molecular weight of from 17 kDa to 30 kDa,for example the endoglucanases sold under the tradename Biotouch® NCD,DCC and DCL (AB Enzymes, Darmstadt, Germany).

Suitable cellulases may also exhibit xyloglucanase activity, such asWhitezyme®.

Lipase.

The composition may comprise a lipase. Suitable lipases include those ofbacterial or fungal origin. Chemically modified or protein engineeredmutants are included. Examples of useful lipases include lipases fromHumicola (synonym Thermomyces), e.g., from H. lanuginosa (T.lanuginosus), or from H. insolens, a Pseudomonas lipase, e.g., from P.alcaligenes or P. pseudoalcaligenes, P. cepacia, P. stutzeri, P.fluorescens, Pseudomonas sp. strain SD 705, P. wisconsinensis, aBacillus lipase, e.g., from B. subtilis, B. stearothermophilus or B.pumilus.

The lipase may be a “first cycle lipase”, optionally a variant of thewild-type lipase from Thermomyces lanuginosus comprising T231R and N233Rmutations. The wild-type sequence is the 269 amino acids (amino acids23-291) of the Swissprot accession number Swiss-Prot O59952 (derivedfrom Thermomyces lanuginosus (Humicola lanuginosa)). Suitable lipaseswould include those sold under the tradenames Lipex®, Lipolex® andLipoclean® by Novozymes, Bagsvaerd, Denmark.

The composition may comprise a variant of Thermomyces lanuginosa(O59952) lipase having >90% identity with the wild type amino acid andcomprising substitution(s) at T231 and/or N233, optionally T231R and/orN233R.

Xyloglucanase:

Suitable xyloglucanase enzymes may have enzymatic activity towards bothxyloglucan and amorphous cellulose substrates. The enzyme may be aglycosyl hydrolase (GH) selected from GH families 5, 12, 44 or 74. Theglycosyl hydrolase selected from GH family 44 is particularly suitable.Suitable glycosyl hydrolases from GH family 44 are the XYG1006 glycosylhydrolase from Paenibacillus polyxyma (ATCC 832) and variants thereof.

Pectate Lyase:

Suitable pectate lyases are either wild-types or variants ofBacillus-derived pectate lyases (CAF05441, AAU25568) sold under thetradenames Pectawash®, Pectaway® and X-Pect® (from Novozymes A/S,Bagsvaerd, Denmark).

Mannanase:

Suitable mannanases are sold under the tradenames Mannaway® (fromNovozymes A/S, Bagsvaerd, Denmark), and Purabrite® (GenencorInternational Inc., Palo Alto, Calif.).

Bleaching Enzyme:

Suitable bleach enzymes include oxidoreductases, for example oxidasessuch as glucose, choline or carbohydrate oxidases, oxygenases,catalases, peroxidases, like halo-, chloro-, bromo-, lignin-, glucose-or manganese-peroxidases, dioxygenases or laccases (phenoloxidases,polyphenoloxidases). Suitable commercial products are sold under theGuardzyme® and Denilite® ranges from Novozymes. It may be advantageousfor additional organic compounds, especially aromatic compounds, to beincorporated with the bleaching enzyme; these compounds interact withthe bleaching enzyme to enhance the activity of the oxidoreductase(enhancer) or to facilitate the electron flow (mediator) between theoxidizing enzyme and the stain typically over strongly different redoxpotentials.

Other suitable bleaching enzymes include perhydrolases, which catalysethe formation of peracids from an ester substrate and peroxygen source.Suitable perhydrolases include variants of the Mycobacterium smegmatisperhydrolase, variants of so-called CE-7 perhydrolases, and variants ofwild-type subtilisin Carlsberg possessing perhydrolase activity.

Cutinase:

Suitable cutinases are defined by E.C. Class 3.1.1.73, optionallydisplaying at least 90%, or 95%, or most optionally at least 98%identity with a wild-type derived from one of Fusarium solani,Pseudomonas Mendocina or Humicola Insolens.

Identity.

The relativity between two amino acid sequences is described by theparameter “identity”. For purposes of the present invention, thealignment of two amino acid sequences is determined by using the Needleprogram from the EMBOSS package (http://emboss.org) version 2.8.0. TheNeedle program implements the global alignment algorithm described inNeedleman, S. B. and Wunsch, C. D. (1970) J. Mol. Biol. 48, 443-453. Thesubstitution matrix used is BLOSUM62, gap opening penalty is 10, and gapextension penalty is 0.5.

Fabric-Softener:

Suitable fabric-softening agents include clay, silicone and/orquaternary ammonium compounds. Suitable clays include montmorilloniteclay, hectorite clay and/or laponite clay. A suitable clay ismontmorillonite clay. Suitable silicones include amino-silicones and/orpolydimethylsiloxane (PDMS). A suitable fabric softener is a particlecomprising clay and silicone, such as a particle comprisingmontmorillonite clay and PDMS.

Flocculant:

Suitable flocculants include polyethylene oxide; for example having anaverage molecular weight of from 300,000 Da to 900,000 Da.

Suds Suppressor:

Suitable suds suppressors include silicone and/or fatty acid such asstearic acid.

Perfume:

Suitable perfumes include perfume microcapsules, polymer assistedperfume delivery systems including Schiff base perfume/polymercomplexes, starch-encapsulated perfume accords, perfume-loaded zeolites,blooming perfume accords, and any combination thereof. A suitableperfume microcapsule is melamine formaldehyde based, typicallycomprising perfume that is encapsulated by a shell comprising melamineformaldehyde. It may be highly suitable for such perfume microcapsulesto comprise cationic and/or cationic precursor material in the shell,such as polyvinyl formamide (PVF) and/or cationically modifiedhydroxyethyl cellulose (catHEC).

Aesthetic:

Suitable aesthetic particles include soap rings, lamellar aestheticparticles, geltin beads, carbonate and/or sulphate salt speckles,coloured clay particles, and any combination thereof.

Methods for Forming the Laundry Detergent Particle:

One method for forming the laundry detergent particle, or hueingparticle, of the present invention includes the steps of providing aclay carrier, loading the carrier into a rotating drum or other suitablemechanical device.

The hueing agent, or coloring agent, optionally with a suitable diluent,is then added to the clay carrier in the rotating drum. The hueing agentmay be added to the drum using any conventional means for addingmaterials to a container. For example, the hueing agent may be sprayedinto the drum. The hueing agent thus comes into contact with the claycarrier to form a laundry detergent particle, or hueing particle. Thehueing agent may provide a substantially uniform coating on and/or intothe clay carrier. The resulting hueing particle may have a finalcolor-on-speckle loading of 0.01% to 10%, more preferably of 0.1% to 5%.

The hueing particles may then be dried. Drying may be accomplished byany conventional means known for drying particulate materials.

The general methods for preparing the hueing particles described hereinmay not be construed as limiting the scope of the present invention. Itshould be possible, by way of alternative processing methods, to combinethe hueing agent and clay carrier to produce a hueing particle whichexhibits similar non-staining properties, as well as other desiredfeatures, as the hueing particles produced by the general methodsdescribed herein and by their equivalent methods as known to thoseskilled in the art. For instance, it may be possible to combine the claycarrier and hueing agent together in one step.

Method of Laundering Fabric:

The method of laundering fabric typically comprises the step ofcontacting the composition to water to form a wash liquor, andlaundering fabric in said wash liquor, wherein typically the wash liquorhas a temperature of above 0° C. to 90° C., or to 60° C., or to 40° C.,or to 30° C., or to 20° C., or to 10° C., or even to 8° C. The fabricmay be contacted to the water prior to, or after, or simultaneous with,contacting the laundry detergent composition with water. The compositioncan be used in pre-treatment applications.

Typically, the wash liquor is formed by contacting the laundry detergentto water in such an amount so that the concentration of laundrydetergent composition in the wash liquor is from above 0 g/l to 10 g/l,or from 1 g/l, and to 9 g/l, or to 8.0 g/l, or to 7.0 g/l, or to 6.0g/l, or to 4 g/l, or even to 3.0 g/l, or even to 2.5 g/l.

The method of laundering fabric may be carried out in a top-loading orfront-loading automatic washing machine, or can be used in a hand-washlaundry application. In these applications, the wash liquor formed andconcentration of laundry detergent composition in the wash liquor isthat of the main wash cycle. Any input of water during any optionalrinsing step(s) is not included when determining the volume of the washliquor.

The wash liquor may comprise 70 liters or less of water, 55 liters orless of water, 40 liters or less of water, or 30 liters or less, or 20liters or less, or 10 liters or less, or 8 liters or less, or even 6liters or less of water. The wash liquor may comprise from above 0 to 15liters, or from 2 liters, and to 12 liters, or even to 8 liters ofwater.

Typically from 0.01 kg to 2 kg of fabric per liter of wash liquor isdosed into said wash liquor.

Typically from 0.01 kg, or from 0.05 kg, or from 0.07 kg, or from 0.10kg, or from 0.15 kg, or from 0.20 kg, or from 0.25 kg fabric per literof wash liquor is dosed into said wash liquor.

Optionally, 150 g or less, 100 g or less, 50 g or less, or 45 g or less,or 40 g or less, or 35 g or less, or 30 g or less, or 25 g or less, or20 g or less, or even 15 g or less, or even 10 g or less of thecomposition is contacted to water to form the wash liquor.

EXAMPLES Example 1 Suitable Granular Laundry Detergent Compositions

Ingredient Amount (in wt %) Particle in accordance with the presentinvention. From 0.01 wt % to 5 wt % (containing a molecule according toany of the BA formulae given above, in particular BA10, BA20, BA51,BA55, BA56, BA57, BA60, BA66, BA69, BA78) Anionic detersive surfactant(such as alkyl benzene from 8 wt % to 15 wt % sulphonate, alkylethoxylated sulphate and mixtures thereof) Non-ionic detersivesurfactant (such as alkyl ethoxylated from 0.5 wt % to 4 wt % alcohol)Cationic detersive surfactant (such as quaternary from 0 to 4 wt %ammonium compounds) Other detersive surfactant (such as zwiterionicdetersive from 0 wt % to 4 wt % surfactants, amphoteric surfactants andmixtures thereof) Carboxylate polymer (such as co-polymers of maleicacid from 1 wt % to 4 wt % and acrylic acid) Polyethylene glycol polymer(such as a polyethylene glycol from 0.5 wt % to 4 wt % polymercomprising poly vinyl acetate side chains) Polyester soil releasepolymer (such as Repel-o-tex and/or from 0.1 to 2 wt % Texcare polymers)Cellulosic polymer (such as carboxymethyl cellulose, methyl from 0.5 wt% to 2 wt % cellulose and combinations thereof) Other polymer (such asamine polymers, dye transfer from 0 wt % to 4 wt % inhibitor polymers,hexamethylenediamine derivative polymers, and mixtures thereof) Zeolitebuilder and phosphate builder (such as zeolite 4A from 0 wt % to 4 wt %and/or sodium tripolyphosphate) Other builder (such as sodium citrateand/or citric acid) from 0 wt % to 3 wt % Carbonate salt (such as sodiumcarbonate and/or sodium from 15 wt % to 30 wt % bicarbonate) Silicatesalt (such as sodium silicate) from 0 wt % to 10 wt % Filler (such assodium sulphate and/or bio-fillers) from 10 wt % to 40 wt % Source ofavailable oxygen (such as sodium percarbonate) from 10 wt % to 20 wt %Bleach activator (such as tetraacetylethylene diamine from 2 wt % to 8wt % (TAED) and/or nonanoyloxybenzenesulphonate (NOBS) Bleach catalyst(such as oxaziridinium-based bleach catalyst from 0 wt % to 0.1 wt %and/or transition metal bleach catalyst) Other bleach (such as reducingbleach and/or pre-formed from 0 wt % to 10 wt % peracid) Chelant (suchas ethylenediamine-N′N′-disuccinic acid from 0.2 wt % to 1 wt % (EDDS)and/or hydroxyethane diphosphonic acid (HEDP) Photobleach (such as zincand/or aluminium sulphonated from 0 wt % to 0.1 wt % phthalocyanine)Hueing agent (such as direct violet 99, acid red 52, acid blue from 0 wt% to 1 wt % 80, direct violet 9, solvent violet 13 and any combinationthereof) Brightener (C.I. fluorescent brightener 260 or C.I. from 0.1 wt% to 0.4 wt % fluorescent brightener 351) Protease (such as Savinase,Savinase Ultra, Purafect, FN3, from 0.1 wt % to 0.4 wt % FN4 and anycombination thereof) Amylase (such as Termamyl, Termamyl ultra,Natalase, from 0.05 wt % to 0.2 wt % Optisize, Stainzyme, Stainzyme Plusand any combination thereof) Cellulase (such as Carezyme and/orCelluclean) from 0.05 wt % to 0.2 wt % Lipase (such as Lipex, Lipolex,Lipoclean and any from 0.1 to 1 wt % combination thereof) Other enzyme(such as xyloglucanase, cutinase, pectate from 0 wt % to 2 wt % lyase,mannanase, bleaching enzyme) Fabric softener (such as montmorilloniteclay and/or from 0 wt % to 4 wt % polydimethylsiloxane (PDMS) Flocculant(such as polyethylene oxide) from 0 wt % to 1 wt % Suds suppressor (suchas silicone and/or fatty acid) from 0 wt % to 0.1 wt % Perfume (such asperfume microcapsule, spray-on perfume, from 0.1 wt % to 1 wt % starchencapsulated perfume accords, perfume loaded zeolite, and anycombination thereof) Aesthetics (such as coloured soap rings and/orcoloured from 0 wt % to 1 wt % speckles/noodles) Miscellaneous Balance

Example 2 Method for Forming the Particles

Sample 1-0: Large Sodium Bentonite Particles

Natural Sodium Bentonite Granular (AMCOL®) was used as received(typically 2% max>1400 m, 60%-70%>425 μm, 3% max<180 μm) as a referencein testing.

Sample 1-1: Inventive Hueing Agent Large Sodium Bentonite Particles

The dye is a hueing agent having a structure in accordance with thepresent invention.

1. 96.2 g of the natural sodium bentonite material (AMCOL®), as received(typically 2% max>1400 μm, 60%-70%>425 μm, 3% max<180 μm) was put intothe drum of a tumble mixer. The drum continued rotating for the entireprocedure, except for re-incorporation steps, detailed below.2. 3.80 g of the inventive hueing agent solution with a color value of4.6 were weighed out.3. A portion of the inventive hueing agent solution was then sprayedonto the clay carrier material while the drum was rotating.4. The drum was stopped and any material (hueing agent or solid) stuckto the walls/baffles was scrapped off, re-incorporated into the bulk,and the mixer re-tumbled, to ensure that the 1^(st) tranche of spray-onwas homogeneously applied across the carrier, with minimal wallresidues.5. The remaining inventive hueing agent solution was then sprayed-on andhomogeneously spread in multiple tranches, as per steps 3 & 4.6. The hueing particles thus produced were then left in an open plasticbeaker to dry overnight. (Final wt % moisture=3.95%)Sample 1-2: Inventive Hueing Agent Small Bentonite Particles

The dye is a hueing agent having a structure in accordance with thepresent invention.

1. Natural sodium bentonite material (AMCOL®), as received (typically 2%max>1400 μm, 60%-70%>425 μm, 3% max<180 μm) was ground using a coffeegrinder (Braun) to reduce the average particle size. 96.2 g of theresulting sodium bentonite material that was retained by the 106 μmsieve and through the 212 μm sieve was put into the drum of a tumblemixer.2. 3.80 g of the inventive hueing agent solution with a color value of4.6 were weighed out.3. A portion of the inventive hueing agent solution was then sprayedonto the clay carrier material while the drum was rotating.4. The drum was stopped and any material (hueing agent or solid) stuckto the walls/baffles was scrapped off, re-incorporated into the bulk,and the mixer re-tumbled, to ensure that the 1^(st) tranche of spray-onwas homogeneously applied across the carrier, with minimal wallresidues.5. The remaining inventive hueing agent solution was then sprayed-on andhomogeneously spread in multiple tranches, as per steps 3 & 4.6. The hueing particles thus produced were then left in an open plasticbeaker to dry overnight. (Final wt % moisture=˜4%)Sample 1-3: Inventive Hueing Agent Sodium Carbonate Particles

The dye is a hueing agent having a structure in accordance with thepresent invention.

1. 96.2 g of the sodium carbonate granular grade material (Tata) asreceived was put into the drum of a tumble mixer. The drum continuedrotating for the entire procedure except for re-incorporation steps,detailed below.

2. 3.80 g of the inventive hueing agent solution with a color value of4.6 were weighed out

3. A portion of the inventive hueing agent solution was then sprayedonto the sodium carbonate carrier material while the drum was rotating.

4. The drum was stopped and any material (hueing or solid) stuck to thewalls/baffles was scrapped off, re-incorporated into the bulk, and themixer re-tumbled, to ensure that the 1^(st) tranche of spray-on washomogeneously applied across the carrier, with minimal wall residues.5. The remaining inventive hueing agent solution was then sprayed-on andhomogeneously spread in multiple tranches, as per steps 3 & 4.6. The hueing particles thus produced were then left in an open plasticbeaker to dry overnight. (Final wt % moisture<1%)Sample 1-4 Liquitint® Violet DD Large Sodium Bentonite Particles1. 88.6 g of the natural sodium bentonite material (AMCOL®), as received(typically 2% max>1400 μm, 60%-70%>425 μm, 3% max<180 μm) was put intothe drum of a tumble mixer. The drum continued rotating for the entireprocedure, except for re-incorporation steps, detailed below.2. 11.4 g of the Liquitint® Violet DD solution (Milliken, Spartanburg,S.C.) with a color value of 4.5 were weighed out. This amount ofLiquitint® Violet DD solution is required to match the intensity of the3.8 g of the inventive hueing agent solution. This determination wasmade by measuring absorbance at 540 nm by UV-Visible spectroscopy of 100mg of the as received materials in 1 L of deionized water.3. A portion of the Liquitint® Violet DD solution was then sprayed ontothe clay carrier material while the drum was rotating.4. The drum was stopped and any material (hueing agent or solid) stuckto the walls/baffles was scrapped off, re-incorporated into the bulk,and the mixer re-tumbled, to ensure that the 1^(st) tranche of spray-onwas homogeneously applied across the carrier, with minimal wallresidues.5. The remaining Liquitint® Violet DD solution was then sprayed-on andhomogeneously spread in multiple tranches, as per steps 3 & 4.6. The hueing particles thus produced were then left in an open plasticbeaker to dry overnight. (Final wt % moisture=3.95%)Sample 1-5 Liquitint® Violet DD Sodium Carbonate Particles1. 96.2 g of the sodium carbonate granular grade material (Tata) asreceived was put into the drum of a tumble mixer. The drum continuedrotating for the entire procedure except for re-incorporation steps,detailed below.2. 11.4 g of the Liquitint® Violet DD solution (Milliken, Spartanburg,S.C.) with a color value of 4.5 were weighed out. This amount ofLiquitint® Violet DD solution is required to match the intensity of the3.8 g of the inventive hueing agent solution. This determination wasmade by measuring absorbance at 540 nm by UV-Visible spectroscopy of 100mg of the as received materials in 1 L of deionized water.3. A portion of the Liquitint® Violet DD solution was then sprayed ontothe sodium carbonate carrier material while the drum was rotating.4. The drum was stopped and any material (hueing or solid) stuck to thewalls/baffles was scrapped off, re-incorporated into the bulk, and themixer re-tumbled, to ensure that the 1^(st) tranche of spray-on washomogeneously applied across the carrier, with minimal wall residues.5. The remaining Liquitint® Violet DD solution was then sprayed-on andhomogeneously spread in multiple tranches, as per steps 3 & 46. The hueing particles thus produced were then left in an open plasticbeaker to dry overnight. (Final wt % moisture 9.58%)

Example 3 Spot Staining Evaluation of Particles in a DetergentComposition

A total of six solid particulate laundry detergent compositions arecreated for testing with the base formula shown in the table below.Hueing particles were then admixed into the composition. Fivecompositions contain 1% of the different hueing particles, Samples 1-1to 1-5, while Sample 1-0 contains the 1% natural sodium bentoniteparticles without any hueing agent.

TABLE 1 Laundry Detergent Composition Ingredient wt % sodium linearalkylbenzene sulfonate 12% alkyl ethoxylate (C14-15, EO7) 1% sodiumcarbonate 53% sodium sulfate 15% sodium silicate 7% citric acid 1%co-polymer of maleic acid and acrylic acid 2% misc & minors 8% Hueingparticle (nil hueing reference or samples 1% 1-1 to 1-5 as specified)

For each composition, a 30×30 cm cotton fabric swatch was dipped intowater (20° C., water hardness of 1.36 mM (3:1 Ca²⁺:Mg²⁺ molar ratio)until fully saturated. Excess water was wrung out by hand. Each fabricswatch is placed on a foil base and 30 g of the finished productcontaining 1% hueing particle was placed onto the swatch and spread toensure full coverage. Swatches were left in ambient conditions forsixteen hours and the excess product was rinsed off by dipping in cleanwater (approximately ten times). The experiment was repeated threetimes. Fabrics were then photographed and assessed visually by an expertgrader. The six fabrics from each experiment were ranked in terms of thedegree of dye spotting. The fabric with the least spotting received ascore of 1, that with the second lowest level of spotting a score of 2,and so on, so that the most spotted fabric had a score of 6. Resultswere then averaged across the three replicates and reported in the tablebelow.

TABLE 2 Spot Staining Evaluation Results Overall Sample (Detergentcomposition + 1% particle) Rank Ordering Sample 1-0 Large SodiumBentonite Particles, nil hue 1 Sample 1-1 Inventive Hueing Agent 3 LargeSodium Bentonite Particles Sample 1-2 Inventive Hueing Agent 2 SmallSodium Bentonite Particles Sample 1-3 Inventive Hueing Agent SodiumCarbonate 6 Particles Sample 1-4 Liquitint ® Violet DD 4 Large SodiumBentonite Particles Sample 1-5 Liquitint ® Violet DD 5 Sodium CarbonateParticles

Example 4 In Use Fabric Hueing Deposition Evaluation

A total of six solid particulate laundry detergent compositions arecreated for testing with the base formula shown in the table below.Hueing particles were then admixed into the composition. Fivecompositions contain 1% of the different hueing particles, Samples 1-1to 1-5, while Sample 1-0 contains the 1% natural sodium bentoniteparticles without any hueing agent.

TABLE 3 Laundry Detergent Composition Ingredient wt % sodium linearalkylbenzene sulfonate 12% alkyl ethoxylate (C14-15, EO7) 1% sodiumcarbonate 53% sodium sulfate 15% sodium silicate 7% citric acid 1%co-polymer of maleic acid and acrylic acid 2% misc & minors 8% Hueingparticle (nil hueing reference or samples 1% 1-1 to 1-5 as specified)

Each composition is run in a Tergotometer Apparatus (Copley Model 800)simulated wash with terry towel and knitted cotton fabrics (Equest)using the following typical conditions: 1.6 g in 0.8 liters of water,2000 ppm dose, 20° C. bath temperature, water hardness of 1.36 mM (3:1Ca²⁺:Mg²⁺ molar ratio), wash time of 15 minutes). Fabrics are rinsedonce for 5 minutes and are dried in ambient conditions in the dark. Eachwash pot contains three fabrics of each type and the test was repeatedthree times with the results averaged.

L*, a* and b* and WI CIE values are measured on each fabric using aHunter LabScan XE reflectance spectrophotometer with D65 illumination,10° observer and UV filter excluded. “L” is a measure of the amount ofwhite or black in a sample; higher “L” values indicate a lighter coloredsample. A measure of the amount of red or green in a sample isdetermined by “a*” values. A measure of the amount of blue or yellow ina sample is determined by “b*” values; lower (more negative) b* valuesindicate more blue on a sample. WI CIE is a measure of whiteness withhigher numbers indicating greater whiteness. The table below shows thedifference in the WI CIE for each sample vs. the nil hue control (Sample1-0).

TABLE 4 In Use Hueing Deposition Evaluation Results Terry Towel, KnittedCotton, Sample Delta WI CIE Delta WI CIE (Detergent composition + 1%particle) vs. Sample 1-0 vs. Sample 1-0 Sample 1-0 Large SodiumBentonite 0.00# 0.00# Particles, nil hue Sample 1-1 Inventive HueingAgent 6.64* 5.11* Large Sodium Bentonite Particles Sample 1-2 InventiveHueing Agent 6.25* 4.95* Small Sodium Bentonite Particles Sample 1-3Inventive Hueing Agent 7.26* 5.58* Sodium Carbonate Particles Sample 1-4Liquitint ® Violet DD 3.41*# 2.45*# Large Sodium Bentonite ParticlesSample 1-5 Liquitint ® Violet DD 3.81*# 1.81*# Sodium CarbonateParticles *The WI CIE difference between this Sample particle and Sample1-0, is statistically significant α = 0.05. #The WI CIE differencebetween this Sample particle and Sample 1-1 is statistically significantat α = 0.05.Conclusion:

The Inventive Hueing Agent bentonite particles (Samples 1-1 and 1-2)show less spotting than the comparative Liquitint® Violet DD bentoniteparticles (Sample 1-4). The Inventive Hueing Agent bentonite particles(Samples 1-1 and 1-2) show a statistically significant increase in WICIE versus the nil hueing control (Sample 1-0) and a statisticallysignificant increase in WI CIE versus the comparative Liquitint® VioletDD bentonite particles (Sample 1-4). The Inventive Hueing Agentbentonite particles (Samples 1-1 and 1-2) also provide less spottingthan the Inventive Hueing Agent carbonate particles (Samples 1-3) andLiquitint® Violet DD carbonate particles (Sample 1-5).

Example 5 Staining Properties of Particles Comprising Various BentonitePowders

Different types of bentonite clay powders were tested to evaluate thestaining properties of the Inventive Hueing Agent. The clay powdersinclude Partially Activated Bentonite Powder, and Natural BentonitePowder; both of which were provided by AMCOL. The “Activated” grades areobtained by treating Ca-Bentonite with soda ash. The “Natural” Bentonitegrade is a Natural Na-Bentonite.

The following test procedure was used to create the hueing particles:

-   1. 30 g of bentonite powder was measured into a small food    processor.-   2. The desired amount of hueing agent, or coloring agent, was    measured out into a small beaker and diluted with 7.2 g of deionized    water.-   3. The colored solution was then blended into the powder a little at    a time. If the powder began to agglomerate the sample, was put into    a 60° C. oven until dry. It was then pulverized in the food    processor. The final powder was passed through a No. 25 sieve.-   4. The materials tested are summarized in the table below.

Color Loading (4.5 absorb) Determined via Sample No. Color/Clay PowderExtraction 1 Inventive Hueing Agent/ 4.03 wt % Natural Na Bentonite 2Inventive Hueing Agent/ 4.27 wt % Partially Activated Bentonite 3Inventive Hueing Agent/ 4.37 wt % 50/50 blend of Natural Sodium &Partially Activated Bentonite

The following test procedure was used to evaluate fabric staining of thehueing particles in the absence of detergent in duplicate runs:

-   1. The test fabric piece (100% white cotton fabric) was spread in a    plastic tub having dimensions of 36×24×6 cm. The fabric piece was    cut to have a length of 36 cm and a width of 24 cm.-   2. 0.5 liters of cold (room temperature) tap water was added to the    tub.-   3. 2 g of the hueing particles from the table above was evenly    sprinkled on the test fabric.-   4. After 90 minutes, the fabric was rinsed twice in a tub of cold    tap water and allowed to air dry.-   5. The fabric was evaluated for any visible stains.

The test results are shown in Table 5 below:

TABLE 5 Staining Results for Inventive Hueing Agent on Various Types ofBentonite Powders Sample No. Color/Clay Powder Amount of Staining 1Inventive Hueing Agent/ Least amount of staining Natural Na Bentonite 2Inventive Hueing Agent/ Greatest amount of staining Partially ActivatedBentonite 3 Inventive Hueing Agent/ Amount of staining between 50/50blend of Natural that observed on Sodium & Partially Sample 1 and Sample2 Activated Bentonite

The test results illustrate that, for equivalent or close to equivalentcolor loading, the staining of the Inventive Hueing Agent on PartiallyActivated Bentonite was significantly worse than that of the InventiveHueing Agent on a 50/50 blend of Partially Activated Bentonite andNatural Sodium Bentonite and on Natural Sodium Bentonite alone. Thedifferences in staining were far greater than could be accounted for bythe small differences in dye loading on the various particles. Thus,there was much less visible staining using hueing particles that containnatural bentonite.

While the test results in Table 5 indicate that natural bentonite claymaterial colored with the inventive hueing agent provides less stainingthan synthetic bentonite clay material colored with the inventive hueingagent for the fabric specimen and test method described herein, itshould be recognized that the hueing agents of the present invention aresuitable for use in coloring both natural and synthetic clay materials.The amount of staining observed using synthetic bentonite materials doesnot preclude it from use in laundry detergent compositions, or in othercompositions where the inclusion of at least one hueing agent isdesired. Specific material selection may be dependent upon thecomposition in which it is incorporated and its end-use.

It should be understood that every maximum numerical limitation giventhroughout this specification includes every lower numerical limitation,as if such lower numerical limitations were expressly written herein.Every minimum numerical limitation given throughout this specificationwill include every higher numerical limitation, as if such highernumerical limitations were expressly written herein. Every numericalrange given throughout this specification will include every narrowernumerical range that falls within such broader numerical range, as ifsuch narrower numerical ranges were all expressly written herein.

The dimensions and values disclosed herein are not to be understood asbeing strictly limited to the exact numerical values recited. Instead,unless otherwise specified, each such dimension is intended to mean boththe recited value and a functionally equivalent range surrounding thatvalue. For example, a dimension disclosed as “40 mm” is intended to mean“about 40 mm.”

Every document cited herein, including any cross referenced or relatedpatent or application, is hereby incorporated herein by reference in itsentirety unless expressly excluded or otherwise limited. The citation ofany document is not an admission that it is prior art with respect toany invention disclosed or claimed herein or that it alone, or in anycombination with any other reference or references, teaches, suggests ordiscloses any such invention. Further, to the extent that any meaning ordefinition of a term in this document conflicts with any meaning ordefinition of the same term in a document incorporated by reference, themeaning or definition assigned to that term in this document shallgovern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A particle consisting of: (a) from 0.0001 wt % to4 wt % of a hueing agent, wherein the hueing agent has the followingstructure:

wherein: R₁ and R₂ are independently selected from the group consistingof: H; alkyl; alkoxy; alkyleneoxy; alkyl capped alkyleneoxy; urea; andamido; R₃ is a substituted aryl group; X is a substituted groupcomprising sulfonamide moiety and optionally an alkyl and/or arylmoiety, and wherein the substituted group comprises at least onealkyleneoxy chain that comprises an average molar distribution of atleast four alkyleneoxy moieties; and (b) the balance, a blend of naturalsodium bentonite clay and a whiter bentonite clay; wherein the whiterbentonite clay is selected from the group consisting of calciumbentonite, synthetic sodium bentonite and mixtures thereof.
 2. Aparticle according to claim 1, wherein the hueing agent has thefollowing structure:

wherein: R₁ and R₂ are independently selected from the group consistingof: H; alkyl; alkoxy; alkyleneoxy; alkyl capped alkyleneoxy; urea; andamido; U is a hydrogen, a substituted or unsubstituted amino group; W isa substituted group comprising an amino moiety and optionally an alkyland/or aryl moiety, and wherein the substituted group comprises at leastone alkyleneoxy chain that comprises an average molar distribution of atleast four alkyleneoxy moieties; Y is a hydrogen or a sulfonic acidmoiety; and Z is a sulfonic acid moiety or an amino group substitutedwith an aryl group or an alkyl group.
 3. A particle according to claim2, wherein R₁ is an alkoxy group and R₂ is an alkyl group.
 4. A particleaccording to claim 3, wherein R₁ is a C₁-C₁₀ alkoxy and R₂ is a C₁-C₁₀alkyl.
 5. A particle according to claim 1, wherein at least 95 wt % ofthe blend of clays has a particle size in the range of from 50micrometers to 2000 micrometers.
 6. A particle according to claim 5,wherein at least 95 wt % of the blend of clays has a particle size inthe range of from 50 micrometers to 1500 micrometers.
 7. A particleaccording to claim 6, wherein at least 95 wt % of the blend of clays hasa particle size in the range of from 50 micrometers to 1000 micrometers.8. A particle according to claim 7, wherein at least 95 wt % of theblend of clays has a particle size in the range of from 50 micrometersto 500 micrometers.
 9. A particle according to claim 8, wherein at least95 wt % of the blend of clays has a particle size in the range of from50 micrometers to 300 micrometers.
 10. A particle according to claim 9,wherein at least 95 wt % of the blend of clays has a particle size inthe range of from 50 micrometers to 200 micrometers.
 11. A particleconsisting of: (a) from 0.0001 wt % to 4 wt % of a hueing agent, whereinthe hueing agent has the following structure:

wherein: R₁ and R₂ are independently selected from the group consistingof: H; alkyl; alkoxy; alkyleneoxy; alkyl capped alkyleneoxy; urea; andamido; R₃ is a substituted aryl group; X is a substituted groupcomprising sulfonamide moiety and optionally an alkyl and/or arylmoiety, and wherein the substituted group comprises at least onealkyleneoxy chain that comprises an average molar distribution of atleast four alkyleneoxy moieties; and (b) the balance, a blend of naturalclay and a whiter bentonite clay; wherein the whiter bentonite clay isselected from the group consisting of calcium bentonite, syntheticsodium bentonite and mixtures thereof.
 12. A particle according to claim11, wherein the natural clay is natural montmorillonite clay.
 13. Aparticle according to claim 11, wherein the natural clay is naturalbentonite clay.
 14. A particle according to claim 11, wherein at least95 wt % of the blend of clays has a particle size in the range of from50 micrometers to 2000 micrometers.
 15. A particle according to claim14, wherein at least 95 wt % of the blend of clays has a particle sizein the range of from 50 micrometers to 200 micrometers.